EP2826803A1 - Polymer containing thiophene-benzene-thiophene unit, preparation method therefor and solar cell device - Google Patents
Polymer containing thiophene-benzene-thiophene unit, preparation method therefor and solar cell device Download PDFInfo
- Publication number
- EP2826803A1 EP2826803A1 EP12870996.1A EP12870996A EP2826803A1 EP 2826803 A1 EP2826803 A1 EP 2826803A1 EP 12870996 A EP12870996 A EP 12870996A EP 2826803 A1 EP2826803 A1 EP 2826803A1
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- EP
- European Patent Office
- Prior art keywords
- thiophene
- benzene
- polymer containing
- organic
- preparing
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- NIKLLBFAZFYRTL-UHFFFAOYSA-N benzene;thiophene Chemical group C=1C=CSC=1.C=1C=CSC=1.C1=CC=CC=C1 NIKLLBFAZFYRTL-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229920000642 polymer Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 36
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 25
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229910052763 palladium Inorganic materials 0.000 claims description 18
- 229940126062 Compound A Drugs 0.000 claims description 17
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 11
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 11
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 claims description 10
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 3
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical group COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 12
- 239000013049 sediment Substances 0.000 description 12
- 239000000872 buffer Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- -1 n-eicosyl Chemical group 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 229920000547 conjugated polymer Polymers 0.000 description 5
- KHQYEMJKTXQBDY-UHFFFAOYSA-N 4,4-bis(4-octylphenyl)indeno[1,2-b]thiophene Chemical compound C(CCCCCCC)C1=CC=C(C=C1)C1(C2=CC=CC=C2C=2SC=CC21)C2=CC=C(C=C2)CCCCCCCC KHQYEMJKTXQBDY-UHFFFAOYSA-N 0.000 description 4
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 0 CC(C)(C)c1cc(C(c2c-3cc(C(c4c-5[s]c(C6=CC=C7c8ccc(C(C)(C)C)cc8C(*)(*)C7(C)C6)c4)(c4ccc(*)cc4)c4ccc(*)cc4)c-5c2)(c2ccc(*)cc2)c2ccc(*)cc2)c-3[s]1 Chemical compound CC(C)(C)c1cc(C(c2c-3cc(C(c4c-5[s]c(C6=CC=C7c8ccc(C(C)(C)C)cc8C(*)(*)C7(C)C6)c4)(c4ccc(*)cc4)c4ccc(*)cc4)c-5c2)(c2ccc(*)cc2)c2ccc(*)cc2)c-3[s]1 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- UCFSYHMCKWNKAH-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OBOC1(C)C UCFSYHMCKWNKAH-UHFFFAOYSA-N 0.000 description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- RVFLMSKITNJVRB-UHFFFAOYSA-N 2-[9,9-dimethyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)fluoren-2-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(C=2C(=CC(=CC=2)B2OC(C)(C)C(C)(C)O2)C2(C)C)C2=C1 RVFLMSKITNJVRB-UHFFFAOYSA-N 0.000 description 1
- FAHIZHKRQQNPLC-UHFFFAOYSA-N 2-[9,9-dioctyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)fluoren-2-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound C1=C2C(CCCCCCCC)(CCCCCCCC)C3=CC(B4OC(C)(C)C(C)(C)O4)=CC=C3C2=CC=C1B1OC(C)(C)C(C)(C)O1 FAHIZHKRQQNPLC-UHFFFAOYSA-N 0.000 description 1
- NQZMILKTJPLYQD-UHFFFAOYSA-N 2-bromo-4,4-bis(4-methylphenyl)indeno[1,2-b]thiophene Chemical compound C1=CC(C)=CC=C1C1(C=2C=CC(C)=CC=2)C2=CC=CC=C2C2=C1C=C(Br)S2 NQZMILKTJPLYQD-UHFFFAOYSA-N 0.000 description 1
- CEPPKKLWDGWJEJ-UHFFFAOYSA-N 2-bromo-4,4-bis(4-octylphenyl)indeno[1,2-b]thiophene Chemical compound BrC1=CC2=C(S1)C1=CC=CC=C1C2(C2=CC=C(C=C2)CCCCCCCC)C2=CC=C(C=C2)CCCCCCCC CEPPKKLWDGWJEJ-UHFFFAOYSA-N 0.000 description 1
- RSYMIIZYGIRASH-UHFFFAOYSA-N BrC1=CC2=C(S1)C1=CC=CC=C1C2(C2=CC=C(C=C2)CCCCCC)C2=CC=C(C=C2)CCCCCC Chemical compound BrC1=CC2=C(S1)C1=CC=CC=C1C2(C2=CC=C(C=C2)CCCCCC)C2=CC=C(C=C2)CCCCCC RSYMIIZYGIRASH-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
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- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
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- H10K85/211—Fullerenes, e.g. C60
- H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present disclosure relates to an optoelectronic field, more particularly relates to a polymer containing thiophene-benzene-thiophene unit, preparation method thereof and solar cell device using the polymer containing thiophene-benzene-thiophene unit.
- the thiophene is a typical electron-deficient unit, thus the polymer containing thiophene-benzene-thiophene unit has high hole mobility and shows an excellent photovoltaic performance.
- the band gap (the energy difference between the HOMO level and the LUMO level) of the conventional polymer containing thiophene-benzene-thiophene unit is relatively wide, which reduces the absorptivity to the photon in the solar spectrum; so that the power conversion efficiency of the solar cell having the polymer containing thiophene-benzene-thiophene unit is low.
- a polymer containing thiophene-benzene-thiophene unit has a formula:
- R 1 represents C 1 to C 20 alkyl
- R 2 represents C 1 to C 20 alkyl
- n is an integer from 10 to 100.
- a method of preparing a polymer containing thiophene-benzene-thiophene unit includes the steps of:
- R 1 represents C 1 to C 20 alkyl
- R 2 represents C 1 to C 20 alkyl
- the compound A and the compound B according to a molar ratio of 1:1 to 1:1.2 are added to an organic solvent containing a catalyst to perform a Suzuki coupling reaction; where the catalyst is organic palladium or a mixture of organic palladium and organic phosphine ligand; then the polymer containing thiophene-benzene-thiophene unit P is obtained: where n is an integer from 10 to 100.
- the organic solvent is at least one selected from the group consisting of toluene, N, N-dimethylformamide, and tetrahydrofuran.
- the organic palladium is selected from the group consisting of bis(triphenylphosphine) palladium(II) dichloride, tetrakis (triphenylphosphine)palladium, and tris(dibenzylideneacetone)dipalladium;
- the organic phosphine ligand is selected from the group consisting of tri-tert-butylphosphine and 2-dicyclohexylphosphino -2',6'-dimethoxybiphenyl; a molar ratio between the organic palladium and the organic phosphine ligand is 1:4 to 1:8.
- a molar ratio between the organic palladium in the catalyst and the compound A is 1:20 to 1:100.
- a reaction temperature of the Suzuki coupling reaction is 70°C to 130°C, a reaction time is 12 to 96 hours.
- a reaction temperature of the Suzuki coupling reaction is 80°C to 110°C.
- the method further includes purifying the polymer containing thiophene-benzene-thiophene unit P, where the step of purifying comprises the steps of:
- methanol is added to a solution obtained by the Suzuki coupling reaction of the compound A and the compound B for precipitating and then filtering;
- a solid obtained from the filtering is extracted with methanol and n-hexane successively; the extracted solid is further extracted with chloroform; and the chloroform solution is collected and the solvent is evaporated to obtain a purified polymer containing thiophene-benzene-thiophene unit P.
- a Soxhlet extractor is used for the extracting.
- a solar cell device includes an active layer, where the active layer is made of a polymer containing thiophene-benzene-thiophene unit P having the following formula: where R 1 represents C 1 to C 20 alkyl, R 2 represents C 1 to C 20 alkyl, n is an integer from 10 to 100.
- the thiophene-benzene-thiophene (TPT) derivative has characteristics of high hole mobility, narrow band gap, high absorption coefficient to the sunlight, and wide absorption range; and fluorene is a compound having the structure of rigid planar biphenyl, it has a high light stability and thermal stability and high hole mobility, thus when the polymer containing thiophene-benzene-thiophene unit and fluorene unit is applied to the solar cell device, the power conversion efficiency can be improved greatly.
- a polymer containing thiophene-benzene-thiophene unit of an embodiment has a formula: where R 1 represents C 1 to C 20 alkyl, R 2 represents C 1 to C 20 alkyl, n is an integer from 10 to 100.
- the thiophene-benzene-thiophene (TPT) derivative has characteristics of high hole mobility, narrow band gap, high absorption coefficient to the sunlight, and wide absorption range; and fluorene is a compound having the structure of rigid planar biphenyl, it has high light stability and thermal stability and high hole mobility, thus when the polymer containing thiophene-benzene-thiophene unit and fluorene is applied to the solar cell device, the power conversion efficiency can be greatly improved.
- a method of preparing the polymer containing thiophene-benzene-thiophene unit includes the steps of:
- Step S1 compounds A and B are provided.
- R 1 represents C 1 to C 20 alkyl.
- the compound A can be synthesized according to the method disclosed in the reference of Macromolecule, 2008,41,5519 or purchased from the market.
- the compound B can be purchased from the market.
- Step S2 the polymer containing thiophene-benzene-thiophene unit P is prepared.
- the compound A and the compound B according to a molar ratio of 1:1 to 1:1.2 are added to an organic solvent containing a catalyst to perform a Suzuki coupling reaction.
- the catalyst is organic palladium or a mixture of organic palladium and organic phosphine ligand, then the polymer containing thiophene-benzene-thiophene unit P is obtained: where R 1 represents C 1 to C 20 alkyl, R 2 represents C 1 to C 20 alkyl, n is an integer from 10 to 100.
- the organic solvent is at least one selected from the group consisting of toluene, N, N-dimethylformamide, and tetrahydrofuran. It should be understood that the organic solution can also be other solvents, as long as it can dissolve the compound A and compound B.
- the organic palladium is selected from the group consisting of bis(triphenylphosphine) palladium(II) dichloride, tetrakis(triphenylphosphine) palladium, and tris(dibenzylideneacetone) dipalladium.
- the organic phosphine ligand is selected from the group consisting of tri-tert-butylphosphine and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl.
- a molar ratio between the organic palladium and the organic phosphine ligand in the mixture of the organic palladium and the organic phosphine ligand is 1:4 to 1:8.
- the catalyst is a mixture of tris(dibenzylideneacetone) dipalladium and tri-tert-butylphosphine.
- the organic palladium and the organic phosphine ligand are not limited to the types as listed, as long as the compound A and compound B can perform the Suzuki coupling reaction catalyzed by the catalyst.
- a molar ratio between the organic palladium in the catalyst and the compound A is 1:20 to 1:100. It should be understood that the molar ratio between the organic palladium and the compound A is not limited to 1:20 to 1:100, as long as a catalytic amount of the catalyst is added to the organic solvent of the compound A and compound B.
- a reaction temperature of the Suzuki coupling reaction is 70°C to 130°C, a reaction time is 12 to 96 hours.
- the reaction temperature of the Suzuki coupling reaction is 80°C to 110°C, the reaction time is 24 to 72 hours. It should be understood that the reaction temperature is not limited to 70°C to 130°C, as long as the compound A and compound B can react; the reaction time is not limited to 12 to 96 hours, as long as the reaction of compound A and compound B is completed.
- Step S3 the polymer containing thiophene-benzene-thiophene unit P is purified.
- Methanol is added to a reaction solution obtained by the Suzuki coupling reaction of the compound A and the compound B for precipitating and then the solution is filtered.
- a solid obtained from the filtering is extracted with methanol and n-hexane successively, then the solid is further extracted with chloroform; and the chloroform solution is collected and the solvent is evaporated to obtain a purified polymer containing thiophene-benzene-thiophene unit P.
- a Soxhlet extractor is used for the extracting.
- the obtained purified polymer containing thiophene-benzene-thiophene unit P is dried at a temperature of 50°C for 24 hours.
- the synthetic route of the method of preparing the polymer containing thiophene-benzene-thiophene unit is relatively simple, the manufacturing cost is reduced.
- the prepared polymer containing thiophene-benzene-thiophene unit has high hole mobility and narrow band gap.
- This example disclosed a poly ⁇ bis (4,4 - bis (4 - n-octyl-phenyl)-indeno[1,2-b]thiophene)-co-9,9 - di-n-octyl fluorene ⁇ (polymer containing thiophene-benzene-thiophene unit P1) with the following formula:
- the polymerization reaction stopped after cooling. 40mL of methanol was added to flask, the reaction solution was precipitated to obtain sediment. The sediment was extracted with methanol and n-hexane successively for 24 hours by a Soxhlet extractor after filtering. The sediment was then extracted by using chloroform as a solvent until the reaction solution was colorless. A chloroform solution was collected and rotary evaporated to obtain a red powder, and finally the red powder was dried under vacuum at a temperature of 50°C for 24 hours to obtain a product with a yield of 72%.
- the poly ⁇ bis (4,4 - bis (4 - n-octyl-phenyl)-indeno[1,2-b]thiophene)-co-9,9 - di-n-octyl fluorene ⁇ of example 1 was tested by UV-visible absorption spectra. The results shown that the conjugated polymer had a wide absorption between 400 ⁇ 750nm, the maximum absorption peak was at about 624nm.
- Sediment was obtained; the sediment was extracted with methanol and n-hexane successively for 24 hours by a Soxhlet extractor after filtering. The sediment was then extracted by using chloroform as a solvent until the reaction solution was colorless. A chloroform solution was collected and rotary evaporated to obtain a red powder, and finally the red powder was filtrated under vacuum for overnight to obtain a product with a yield of 63%.
- Example 2 The poly ⁇ bis (4,4 - bis (4 - methylphenyl) - indeno [1,2-b] thiophene-co-9,9 - di (n-eicosyl) fluorene ⁇ of Example 2 was tested by UV-visible absorption spectra. The results shown that the conjugated polymer had a wide absorption between 400 ⁇ 750nm, the maximum absorption peak was at about 628nm.
- the polymerization reaction stopped after cooling. 40mL of methanol was added to the flask, the reaction solution was precipitated to obtain sediment; the sediment was extracted with methanol and n-hexane successively for 24 hours by a Soxhlet extractor after filtering. The sediment was then extracted by using chloroform as a solvent until the reaction solution was colorless. A chloroform solution was collected and rotary evaporated to obtain a red powder, and finally the red powder was dried under vacuum at a temperature of 50°C for 24 hours to obtain a product with a yield of 87%.
- Example 3 The poly ⁇ bis (4,4- bis (4 - n-eicosyl alkylphenyl) - indeno [1,2-b] thiophene-co-9, 9 - dimethyl-fluorene ⁇ of Example 3 was tested by UV-visible absorption spectra. The results shown that the conjugated polymer had a wide absorption between 400 ⁇ 750 nm, the maximum absorption peak was at about 626nm.
- This example disclosed a poly ⁇ bis (4,4 - bis (4 - n-hexyl-phenyl) - indeno [1,2-b] thiophene-co-9, 9 - bis (n-dodecyl) fluorene ⁇ (polymer containing thiophene-benzene-thiophene unit P4) with the following formula:
- the mixed solution was dropped to 50ml of methanol for precipitation after cooling to room temperature. Sediment was obtained; the sediment was extracted with methanol and n-hexane successively for 24 hours by a Soxhlet extractor after filtering. The sediment was then extracted by using chloroform as a solvent until the reaction solution was colorless. A chloroform solution was collected and rotary evaporated to obtain a red powder, and finally the red powder was filtrated under vacuum for overnight to obtain a product with a yield of 68%.
- Example 4 The poly ⁇ bis (4,4 - bis (4 - n-hexyl-phenyl) - indeno [1,2-b] thiophene-co-9, 9 - bis (n-dodecyl) fluorene ⁇ of Example 4 was tested by UV-visible absorption spectra. The results shown that the conjugated polymer has a wide absorption between 400 ⁇ 750nm, the maximum absorption peak was at about 622nm.
- a solar cell device 50 includes a substrate 51, an anode 52, a buffer layer 53, an active layer 54, and a cathode 55.
- the anode 52, the buffer layer 53, the active layer 54, and the cathode 55 are formed sequentially on the substrate 51.
- the substrate 51 is made of glass.
- the anode 52 is formed on a side of the substrate 51.
- the anode 52 is made of ITO (indium tin oxide).
- the ITO has a sheet resistance of 10 to 20 ⁇ /sq.
- the buffer layer 53 is formed on a side of the anode 52 away from the substrate 51.
- the buffer layer 53 is made of a composite of poly 3, 4-ethylenedioxythiophene and poly styrene sulfonate (PEDOT: PSS).
- the active layer 54 is formed on a side of the buffer layer 53 away from the anode 52.
- the active layer 54 includes an electron donor material and an electron acceptor material.
- a molar ratio of the electron donor material and the electron acceptor material is 1:2.
- the electron acceptor material can be (6, 6) - phenyl - C 61 - butyric acid methyl ester (PCBM).
- the electron donor material is the polymer containing thiophene-benzene-thiophene unit P.
- the electron donor material is poly ⁇ bis (4,4 - bis (4 - n-octyl-phenyl) - indeno[1,2-b]thiophene)-co-9,9 - di-n-octyl fluorene ⁇ obtained from the example 1.
- the cathode 55 is formed on a side of the active layer 54 away from the buffer layer 53.
- the cathode 55 can be an aluminum electrode or a double-layer metal electrode, such as Ca/Al or Ba/Al and so on; the thickness of the cathode 55 is preferably 150nm, 35nm, 120mm, or 70nm.
- the cathode 55 is made of aluminum, and the thickness of the cathode 55 is 150nm.
- the buffer layer 53 can be omitted, and then the active layer 54 is formed directly on the surface of the anode 52.
- the manufacturing processes of the solar cell device 50 were shown as follows:
- the anode 52 was formed on a side of the substrate 51; then cleaned by ultrasonic and treated with an oxygen-Plasma; then the anode 52 was coated with a layer of PEDOT: PSS for modification to form the buffer layer 53.
- the active layer 54 was coated on the buffer layer 53.
- the active layer 54 included an electron donor material and an electron acceptor material.
- the electron acceptor material was PCBM.
- the electron donor material was the poly ⁇ bis (4,4-bis(4-n-octyl-phenyl)- indeno [1,2-b] thiophene)-co-9,9 - di-n-octyl fluorene ⁇ obtained from the example 1.
- the cathode 55 was deposited on the active layer 54.
- the cathode 55 was an aluminum layer formed by vacuum deposition.
- the thickness of the cathode 55 was 150nm.
- the solar cell device 50 was heated at 110°C for 4 hours in a sealed condition, and then cooled to room temperature.
- the anneal of the solar cell device can effectively increase the arranged orderliness and regularity of each group in the molecule and the molecular chain segments, and the carrier mobility and the efficiency of the transmission speed were improved, thereby improving the photoelectric conversion efficiency.
- the power conversion efficiency of the bulk-heterojunction solar cell device 50 using the polymer of example 1 as the electron donor material is 4.5%
- the solar cell device 50 When the solar cell device 50 is in use, under illumination, the light is transmitted through the substrate 51 and the anode 52, then the light energy is absorbed by the hole-conduction type electroluminescent material of the active layer 54, thus generating excitons.
- the excitons migrate to the interface between the electron donor and acceptor materials, and the electrons are transferred to the electron acceptor material, such as PCBM, the charges are separated, thereby forming the free carriers, i.e. the free electrons and the holes.
- the free electrons are transferred to the cathode 55 along the electron acceptor material and collected by the cathode; the free holes are transferred to the anode 52 along the electron donor material and collected by the anode 52, thereby forming the photocurrent and photovoltage, and photoelectric conversion is implemented.
- the device When a load is connected, the device is capable of supplying power. Since the hole-conduction type electroluminescent material has a wide spectral response range, the light energy is fully utilized to gain much higher photoelectric conversion efficiency, and the power generation capacity of the organic solar cell is increased. Moreover, this type organic material is also capable of reducing the weight of the organic solar cell; and it can be made by spin-coating and other technologies for mass production.
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Abstract
Description
- The present disclosure relates to an optoelectronic field, more particularly relates to a polymer containing thiophene-benzene-thiophene unit, preparation method thereof and solar cell device using the polymer containing thiophene-benzene-thiophene unit.
- Energy issues are the serious concern of all countries in the world. Solar energy is the best alternative energy for mankind in the future, how to convert solar energy into electrical power is a hotspot in research. In recent years, the popular conjugated polymer thin film organic solar cells have advantages of low cost, light weight, simple fabrication process, capable of being prepared into flexible devices, etc.. In addition, many kinds of organic materials can be used as the material of the thin film organic solar cells, the thin film organic solar cells have great designability; it is promising to improve the performance of the organic solar cells through the design and optimization of materials.
- In the polymer containing thiophene-benzene-thiophene unit, the thiophene is a typical electron-deficient unit, thus the polymer containing thiophene-benzene-thiophene unit has high hole mobility and shows an excellent photovoltaic performance. However, the band gap (the energy difference between the HOMO level and the LUMO level) of the conventional polymer containing thiophene-benzene-thiophene unit is relatively wide, which reduces the absorptivity to the photon in the solar spectrum; so that the power conversion efficiency of the solar cell having the polymer containing thiophene-benzene-thiophene unit is low.
- Accordingly, it is necessary to provide a polymer containing thiophene-benzene-thiophene unit having high power conversion efficiency.
- In addition, it is necessary to provide a method of preparing a polymer containing thiophene-benzene-thiophene unit.
- In addition, it is necessary to provide a solar cell device having a polymer containing thiophene-benzene-thiophene unit.
-
- where R1 represents C1 to C20 alkyl, R2 represents C1 to C20 alkyl, n is an integer from 10 to 100.
- A method of preparing a polymer containing thiophene-benzene-thiophene unit includes the steps of:
- compounds A and B represented by the following formulas are provided:
in an oxygen-free environment, the compound A and the compound B according to a molar ratio of 1:1 to 1:1.2 are added to an organic solvent containing a catalyst to perform a Suzuki coupling reaction; where the catalyst is organic palladium or a mixture of organic palladium and organic phosphine ligand; then the polymer containing thiophene-benzene-thiophene unit P is obtained: - Preferably, the organic solvent is at least one selected from the group consisting of toluene, N, N-dimethylformamide, and tetrahydrofuran.
- Preferably, the organic palladium is selected from the group consisting of bis(triphenylphosphine) palladium(II) dichloride, tetrakis (triphenylphosphine)palladium, and tris(dibenzylideneacetone)dipalladium; the organic phosphine ligand is selected from the group consisting of tri-tert-butylphosphine and 2-dicyclohexylphosphino -2',6'-dimethoxybiphenyl; a molar ratio between the organic palladium and the organic phosphine ligand is 1:4 to 1:8.
- Preferably, a molar ratio between the organic palladium in the catalyst and the compound A is 1:20 to 1:100.
- Preferably, a reaction temperature of the Suzuki coupling reaction is 70°C to 130°C, a reaction time is 12 to 96 hours.
- Preferably, a reaction temperature of the Suzuki coupling reaction is 80°C to 110°C.
- Preferably, the method further includes purifying the polymer containing thiophene-benzene-thiophene unit P, where the step of purifying comprises the steps of:
- methanol is added to a solution obtained by the Suzuki coupling reaction of the compound A and the compound B for precipitating and then filtering;
- a solid obtained from the filtering is extracted with methanol and n-hexane successively;
the extracted solid is further extracted with chloroform; and
the chloroform solution is collected and the solvent is evaporated to obtain a purified polymer containing thiophene-benzene-thiophene unit P. - Preferably, a Soxhlet extractor is used for the extracting.
-
- In the polymer containing thiophene-benzene-thiophene unit, the thiophene-benzene-thiophene (TPT) derivative has characteristics of high hole mobility, narrow band gap, high absorption coefficient to the sunlight, and wide absorption range; and fluorene is a compound having the structure of rigid planar biphenyl, it has a high light stability and thermal stability and high hole mobility, thus when the polymer containing thiophene-benzene-thiophene unit and fluorene unit is applied to the solar cell device, the power conversion efficiency can be improved greatly.
-
-
FIG. 1 is a flow chart of a method of preparing the polymer containing thiophene-benzene-thiophene unit according to an embodiment; -
FIG. 2 is a schematic, cross-sectional view of a solar cell device according to an embodiment; and -
FIG. 3 shows a UV-visible absorption spectrum of the polymer containing thiophene-benzene-thiophene unit of example 1. - A more detailed description of the polymer containing thiophene-benzene-thiophene unit and a preparation method thereof and an application thereof will be illustrated by reference to specific embodiments and drawings.
-
- In the polymer containing thiophene-benzene-thiophene unit, the thiophene-benzene-thiophene (TPT) derivative has characteristics of high hole mobility, narrow band gap, high absorption coefficient to the sunlight, and wide absorption range; and fluorene is a compound having the structure of rigid planar biphenyl, it has high light stability and thermal stability and high hole mobility, thus when the polymer containing thiophene-benzene-thiophene unit and fluorene is applied to the solar cell device, the power conversion efficiency can be greatly improved.
- Referring to
FIG. 1 , a method of preparing the polymer containing thiophene-benzene-thiophene unit according to an embodiment includes the steps of: - Step S1, compounds A and B are provided.
-
-
- In the illustrated embodiment, the compound A can be synthesized according to the method disclosed in the reference of Macromolecule, 2008,41,5519 or purchased from the market. The compound B can be purchased from the market.
- Step S2, the polymer containing thiophene-benzene-thiophene unit P is prepared.
- In an oxygen-free environment, the compound A and the compound B according to a molar ratio of 1:1 to 1:1.2 are added to an organic solvent containing a catalyst to perform a Suzuki coupling reaction. The catalyst is organic palladium or a mixture of organic palladium and organic phosphine ligand, then the polymer containing thiophene-benzene-thiophene unit P is obtained:
- In the illustrated embodiment, the organic solvent is at least one selected from the group consisting of toluene, N, N-dimethylformamide, and tetrahydrofuran. It should be understood that the organic solution can also be other solvents, as long as it can dissolve the compound A and compound B.
- In the illustrated embodiment, the organic palladium is selected from the group consisting of bis(triphenylphosphine) palladium(II) dichloride, tetrakis(triphenylphosphine) palladium, and tris(dibenzylideneacetone) dipalladium. The organic phosphine ligand is selected from the group consisting of tri-tert-butylphosphine and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl. A molar ratio between the organic palladium and the organic phosphine ligand in the mixture of the organic palladium and the organic phosphine ligand is 1:4 to 1:8. Preferably, the catalyst is a mixture of tris(dibenzylideneacetone) dipalladium and tri-tert-butylphosphine. It should be understood that the organic palladium and the organic phosphine ligand are not limited to the types as listed, as long as the compound A and compound B can perform the Suzuki coupling reaction catalyzed by the catalyst.
- In the illustrated embodiment, a molar ratio between the organic palladium in the catalyst and the compound A is 1:20 to 1:100. It should be understood that the molar ratio between the organic palladium and the compound A is not limited to 1:20 to 1:100, as long as a catalytic amount of the catalyst is added to the organic solvent of the compound A and compound B.
- In the illustrated embodiment, a reaction temperature of the Suzuki coupling reaction is 70°C to 130°C, a reaction time is 12 to 96 hours. Preferably, the reaction temperature of the Suzuki coupling reaction is 80°C to 110°C, the reaction time is 24 to 72 hours. It should be understood that the reaction temperature is not limited to 70°C to 130°C, as long as the compound A and compound B can react; the reaction time is not limited to 12 to 96 hours, as long as the reaction of compound A and compound B is completed.
- Step S3, the polymer containing thiophene-benzene-thiophene unit P is purified.
- Methanol is added to a reaction solution obtained by the Suzuki coupling reaction of the compound A and the compound B for precipitating and then the solution is filtered. A solid obtained from the filtering is extracted with methanol and n-hexane successively, then the solid is further extracted with chloroform; and the chloroform solution is collected and the solvent is evaporated to obtain a purified polymer containing thiophene-benzene-thiophene unit P.
- In the illustrated embodiment, a Soxhlet extractor is used for the extracting.
- In the illustrated embodiment, after the chloroform solution is collected and the solvent is evaporated, the obtained purified polymer containing thiophene-benzene-thiophene unit P is dried at a temperature of 50°C for 24 hours.
- The synthetic route of the method of preparing the polymer containing thiophene-benzene-thiophene unit is relatively simple, the manufacturing cost is reduced. The prepared polymer containing thiophene-benzene-thiophene unit has high hole mobility and narrow band gap.
- The specific examples are shown as follows.
-
- The preparation process of the polymer containing thiophene-benzene-thiophene unit P1 was shown as follow:
- Under the protection of nitrogen, bis (2 - bromo -4,4 - bis (4 - n-octyl-phenyl)- indeno [1,2-b] thiophene (353mg, 0.3mmol), 2,2'-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxabo rolane) (193mg, 0.3mmol), tris(dibenzylideneacetone)dipalladium (13.75mg, 0.015mmol), and tri-tert-butylphosphine (24.2mg, 0.12mmol) were dissolved in 12ml of toluene, and a potassium carbonate solution (3 mL, 2mol/L) was added to the solution, then nitrogen was sufficiently introduced to exhaust the air for approximately 30 minutes, the reaction lasted for 48 hours at a temperature of 95°C in the condition of stirring. The polymerization reaction stopped after cooling. 40mL of methanol was added to flask, the reaction solution was precipitated to obtain sediment. The sediment was extracted with methanol and n-hexane successively for 24 hours by a Soxhlet extractor after filtering. The sediment was then extracted by using chloroform as a solvent until the reaction solution was colorless. A chloroform solution was collected and rotary evaporated to obtain a red powder, and finally the red powder was dried under vacuum at a temperature of 50°C for 24 hours to obtain a product with a yield of 72%.
-
- Test results of molecular weight were: Molecular weight (GPC, THF, R.I): Mn =74.2kDa, Mw /Mn =2.2.
- Referring to
FIG. 3 , the poly {bis (4,4 - bis (4 - n-octyl-phenyl)-indeno[1,2-b]thiophene)-co-9,9 - di-n-octyl fluorene} of example 1 was tested by UV-visible absorption spectra. The results shown that the conjugated polymer had a wide absorption between 400∼750nm, the maximum absorption peak was at about 624nm. -
- The preparation process of the polymer containing thiophene-benzene-thiophene unit P2 was shown as follow:
- Under the protection of nitrogen, bis (2 - bromo -4,4 - bis (4 - methylphenyl) - indeno [1,2-b] thiophene) (157 mg, 0.2mmol), 2,2'-9,9 - di (n-eicosyl) fluorene -2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (176mg, 0.22mmol), and 15ml of N, N-dimethylformamide were added to a flask, and a potassium carbonate solution (2mL, 2mol/L) was added to the solution; then the flask was evacuated to remove the oxygen and the nitrogen was introduced sufficiently to the flask, then bis(triphenylphosphine) palladium(II) dichloride (5.6mg,0.008mmol) was added, the solution was heated to 120°C to react for 36 hours; the mixed solution was dropped to 50ml of methanol for precipitation after cooling to room temperature. Sediment was obtained; the sediment was extracted with methanol and n-hexane successively for 24 hours by a Soxhlet extractor after filtering. The sediment was then extracted by using chloroform as a solvent until the reaction solution was colorless. A chloroform solution was collected and rotary evaporated to obtain a red powder, and finally the red powder was filtrated under vacuum for overnight to obtain a product with a yield of 63%.
-
- Test results of molecular weight were: Molecular weight (GPC, THF, R.I): Mn =58.1kDa, Mw /Mn =2.3.
- The poly {bis (4,4 - bis (4 - methylphenyl) - indeno [1,2-b] thiophene-co-9,9 - di (n-eicosyl) fluorene} of Example 2 was tested by UV-visible absorption spectra. The results shown that the conjugated polymer had a wide absorption between 400∼750nm, the maximum absorption peak was at about 628nm.
-
- The preparation process of the polymer containing thiophene-benzene-thiophene unit P3 was shown as follow:
- Under the protection of nitrogen, bis (2 - bromo -4,4 - bis (4 - n-eicosyl alkylphenyl) - indeno [1,2-b] thiophene) (555 mg, 0.3 mmol), 2,2'-(9,9-dimethyl-fluorene -2,7-diyl)bis (4,4,5,5-tetramethyl- 1,3,2-dioxaborolane) (134 mg, 0.36 mmol), and 15ml of tetrahydrofuran were added to a 50mL of 2-necked flask, respectively; nitrogen was sufficiently introduced to exhaust the air for approximately 20 minutes; then tetrakis(triphenylphosphine)palladium (4 mg, 0.003mmol) was added, and a potassium carbonate solution (3mL, 2mol/L) was added to the solution, then nitrogen was introduced sufficiently to exhaust the air for approximately 10 minutes, the reaction lasted for 96 hours at a temperature of 70°C in the condition of stirring. The polymerization reaction stopped after cooling. 40mL of methanol was added to the flask, the reaction solution was precipitated to obtain sediment; the sediment was extracted with methanol and n-hexane successively for 24 hours by a Soxhlet extractor after filtering. The sediment was then extracted by using chloroform as a solvent until the reaction solution was colorless. A chloroform solution was collected and rotary evaporated to obtain a red powder, and finally the red powder was dried under vacuum at a temperature of 50°C for 24 hours to obtain a product with a yield of 87%.
-
- Test results of molecular weight were: Molecular weight (GPC, THF, R.I): Mn =87.8 kDa, Mw /Mn =2.1.
- The poly {bis (4,4- bis (4 - n-eicosyl alkylphenyl) - indeno [1,2-b] thiophene-co-9, 9 - dimethyl-fluorene} of Example 3 was tested by UV-visible absorption spectra. The results shown that the conjugated polymer had a wide absorption between 400∼750 nm, the maximum absorption peak was at about 626nm.
-
- The preparation process of the polymer containing thiophene-benzene-thiophene unit P4 was shown as follow:
- Under the protection of nitrogen, bis (2 - bromo -4,4 - bis (4 - n-hexyl-phenyl) - indeno [1,2-b] thiophene) (213 mg, 0.2mmol), 2,2'-(9,9-n-eicosyl -fluorene -2,7-diyl)bis (4,4,5,5-tetramethyl- 1,3,2- dioxaborolane) (181 mg, 0.24 mmol), and 15ml of N, N-dimethylformamide were added to a flask; and a potassium carbonate solution (2mL, 2mol/L) was added to the solution; then the flask was evacuated to remove the oxygen and the nitrogen was introduced, then bis(triphenylphosphine) palladium(II) dichloride (7.2mg, 0.01 mmol) was added, the solution was heated to 130°C to react for 24 hours. The mixed solution was dropped to 50ml of methanol for precipitation after cooling to room temperature. Sediment was obtained; the sediment was extracted with methanol and n-hexane successively for 24 hours by a Soxhlet extractor after filtering. The sediment was then extracted by using chloroform as a solvent until the reaction solution was colorless. A chloroform solution was collected and rotary evaporated to obtain a red powder, and finally the red powder was filtrated under vacuum for overnight to obtain a product with a yield of 68%.
-
- Test results of molecular weight were: Molecular weight (GPC, THF, R.I):Mn =51.0kDa, Mw /Mn =2.3.
- The poly {bis (4,4 - bis (4 - n-hexyl-phenyl) - indeno [1,2-b] thiophene-co-9, 9 - bis (n-dodecyl) fluorene} of Example 4 was tested by UV-visible absorption spectra. The results shown that the conjugated polymer has a wide absorption between 400∼750nm, the maximum absorption peak was at about 622nm.
- Referring to
FIG. 2 , asolar cell device 50 includes asubstrate 51, ananode 52, abuffer layer 53, anactive layer 54, and acathode 55. Theanode 52, thebuffer layer 53, theactive layer 54, and thecathode 55 are formed sequentially on thesubstrate 51. - In the illustrated embodiment, the
substrate 51 is made of glass. - The
anode 52 is formed on a side of thesubstrate 51. In the illustrated embodiment, theanode 52 is made of ITO (indium tin oxide). Preferably, the ITO has a sheet resistance of 10 to 20Ω/sq. - The
buffer layer 53 is formed on a side of theanode 52 away from thesubstrate 51. Thebuffer layer 53 is made of a composite of poly 3, 4-ethylenedioxythiophene and poly styrene sulfonate (PEDOT: PSS). - The
active layer 54 is formed on a side of thebuffer layer 53 away from theanode 52. Theactive layer 54 includes an electron donor material and an electron acceptor material. A molar ratio of the electron donor material and the electron acceptor material is 1:2. The electron acceptor material can be (6, 6) - phenyl - C61 - butyric acid methyl ester (PCBM). The electron donor material is the polymer containing thiophene-benzene-thiophene unit P. In the illustrated embodiment, the electron donor material is poly {bis (4,4 - bis (4 - n-octyl-phenyl) - indeno[1,2-b]thiophene)-co-9,9 - di-n-octyl fluorene} obtained from the example 1. - The
cathode 55 is formed on a side of theactive layer 54 away from thebuffer layer 53. Thecathode 55 can be an aluminum electrode or a double-layer metal electrode, such as Ca/Al or Ba/Al and so on; the thickness of thecathode 55 is preferably 150nm, 35nm, 120mm, or 70nm. In the illustrated embodiment, thecathode 55 is made of aluminum, and the thickness of thecathode 55 is 150nm. - It can be understood that, the
buffer layer 53 can be omitted, and then theactive layer 54 is formed directly on the surface of theanode 52. - The manufacturing processes of the
solar cell device 50 were shown as follows: - The
anode 52 was formed on a side of thesubstrate 51; then cleaned by ultrasonic and treated with an oxygen-Plasma; then theanode 52 was coated with a layer of PEDOT: PSS for modification to form thebuffer layer 53. - The
active layer 54 was coated on thebuffer layer 53. Theactive layer 54 included an electron donor material and an electron acceptor material. The electron acceptor material was PCBM. The electron donor material was the poly {bis (4,4-bis(4-n-octyl-phenyl)- indeno [1,2-b] thiophene)-co-9,9 - di-n-octyl fluorene} obtained from the example 1. - The
cathode 55 was deposited on theactive layer 54. In the illustrated embodiment, thecathode 55 was an aluminum layer formed by vacuum deposition. The thickness of thecathode 55 was 150nm. - In the illustrated embodiment, the
solar cell device 50 was heated at 110°C for 4 hours in a sealed condition, and then cooled to room temperature. The anneal of the solar cell device can effectively increase the arranged orderliness and regularity of each group in the molecule and the molecular chain segments, and the carrier mobility and the efficiency of the transmission speed were improved, thereby improving the photoelectric conversion efficiency. - Under the AM1.5G100 mW/cm2 illumination, the power conversion efficiency of the bulk-heterojunction
solar cell device 50 using the polymer of example 1 as the electron donor material is 4.5%, - When the
solar cell device 50 is in use, under illumination, the light is transmitted through thesubstrate 51 and theanode 52, then the light energy is absorbed by the hole-conduction type electroluminescent material of theactive layer 54, thus generating excitons. The excitons migrate to the interface between the electron donor and acceptor materials, and the electrons are transferred to the electron acceptor material, such as PCBM, the charges are separated, thereby forming the free carriers, i.e. the free electrons and the holes. The free electrons are transferred to thecathode 55 along the electron acceptor material and collected by the cathode; the free holes are transferred to theanode 52 along the electron donor material and collected by theanode 52, thereby forming the photocurrent and photovoltage, and photoelectric conversion is implemented. When a load is connected, the device is capable of supplying power. Since the hole-conduction type electroluminescent material has a wide spectral response range, the light energy is fully utilized to gain much higher photoelectric conversion efficiency, and the power generation capacity of the organic solar cell is increased. Moreover, this type organic material is also capable of reducing the weight of the organic solar cell; and it can be made by spin-coating and other technologies for mass production. - Although the present invention has been described with reference to the embodiments thereof and the best modes for carrying out the present invention, it is apparent to those skilled in the art that a variety of modifications and changes may be made without departing from the scope of the present invention, which is intended to be defined by the appended claims.
Claims (10)
- A method of preparing a polymer containing thiophene-benzene-thiophene unit, comprising the steps of:providing compounds A and B represented by the following formulas:
- The method of preparing a polymer containing thiophene-benzene-thiophene unit according to claim 2, wherein the organic solvent is at least one selected from the group consisting of toluene, N, N-dimethylformamide, and tetrahydrofuran.
- The method of preparing a polymer containing thiophene-benzene-thiophene unit according to claim 2, wherein the organic palladium is selected from the group consisting of bis(triphenylphosphine) palladium(II) dichloride, tetrakis(triphenylphosphine)palladium, and tris(dibenzylideneacetone)dipalladium; the organic phosphine ligand is selected from the group consisting of tri-tert-butylphosphine and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl; a molar ratio between the organic palladium and the organic phosphine ligand is 1:4 to 1:8.
- The method of preparing a polymer containing thiophene-benzene-thiophene unit according to claim 2, wherein a molar ratio between the organic palladium in the catalyst and the compound A is 1:20 to 1:100.
- The method of preparing a polymer containing thiophene-benzene-thiophene unit according to claim 2, wherein a reaction temperature of the Suzuki coupling reaction is 70°C to 130°C, a reaction time is 12 to 96 hours.
- The method of preparing a polymer containing thiophene-benzene-thiophene unit according to claim 2, wherein a reaction temperature of the Suzuki coupling reaction is 80°C to 110°C.
- The method of preparing a polymer containing thiophene-benzene-thiophene unit according to claim 2, further comprising:purifying the polymer containing thiophene-benzene-thiophene unit P,wherein the step of purifying comprises the steps of:adding methanol to a solution obtained by the Suzuki coupling reaction of the compound A and the compound B for precipitating and then filtering;extracting a solid obtained from the filtering with methanol and n-hexane successively;extracting the extracted solid with chloroform; andcollecting the chloroform solution and evaporating the solvent to obtain a purified polymer containing thiophene-benzene-thiophene unit P.
- The method of preparing a polymer containing thiophene-benzene-thiophene unit according to claim 8, wherein a Soxhlet extractor is used for the extracting.
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PCT/CN2012/072216 WO2013134913A1 (en) | 2012-03-12 | 2012-03-12 | Polymer containing thiophene-benzene-thiophene unit, preparation method therefor and solar cell device |
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CN113683755A (en) * | 2021-08-20 | 2021-11-23 | 中国科学院上海微系统与信息技术研究所 | Thiophene fluorescent compound, preparation method and methamphetamine detection method |
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JP2008255097A (en) * | 2007-03-09 | 2008-10-23 | Sumitomo Chemical Co Ltd | Fluorine-containing polycyclic aromatic compound, fluorine-containing polymer, organic thin film and organic thin film element |
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US9017577B2 (en) * | 2008-08-18 | 2015-04-28 | Merck Patent Gmbh | Indacenodithiophene and indacenodiselenophene polymers and their use as organic semiconductors |
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CN102286141B (en) * | 2010-06-18 | 2012-10-03 | 海洋王照明科技股份有限公司 | Organic semiconductor material containing fluorene, anthracene and thiophene bithiophene, preparation method thereof and application thereof |
EP2586809B1 (en) * | 2010-06-23 | 2016-08-10 | Ocean's King Lighting Science&Technology Co., Ltd. | Polymer containing units of fluorene, anthracene and benzothiadiazole, preparation method and uses thereof |
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